Quinonimide dyestuffs and the process of making the same



Patented Aug. 25, 1925.

Units!) STATES PATENT o-rmcs.

APQTHUR ononon oasnu, KENNETH Hanannr sauunnns, AND ERNEST BRYAN ADAMS, or MANCHESTER, ENoLum. I

Qumonmmn DYESTUFFS AND Tnnrnoosss or MAKING rnn shun R Drawing.

To all whom it may concern:

Be it' known that we, ARTHUP GEORGE .,GREEN, KENNETH HERBERT Smunaas, and Enrmsr BRYAN ADAMS, all of Crumpsall Vale Chemical Works, Blackley, Manchester, England, all subjects of th King of Great Britain and Ireland, have invented ponents are obtained by the action of sulphuric acid upon the corresponding hydroxyethyl-compounds, the latter being produced by condensation of ethylene chlorhydrin with amido bodies.

In the complete specification of the said British Patent No. 181,750 we have further shown that colouring-matters and intermediates containing the sulphatogropyl- C H, .SO,H, suiphatohutyP-QH .S-O,H, or analogous group, vare also obtainable by similar reactions using other chlorhydrins, and likewise have acid-dyeing properties.

In the course of our investigations in this field we have invented a number of new colouring-matters and intermediates containing the hydroxyethyl, hydroxyp ropyl,

- hyrhoxyhutyl or analogous grout), which on treatment with sulphuric acid are readily converted into the sulphatocompounds which are soluble acid dyestufl's which split off l-l. ,S() upon hydrolysis. These are not merely useful for conversion into'sulphato compounds, but are in Qthemselves useful dyestuffs or components for dyestuffs, ofier ing advantages over the. corresponding alkylated compounds not only in ease of manufacture but also in their properties.

The present invention relates to the manufacture of suchhydroxyalkylated dyestuffs,

as posscx a quinonimide structure. Such dyestuffs may possess basic properties or may contain sulphonic acid or mordant dye- Ahplication filed April 4,

1922; Serial mi. 549,541;

ing groups the constitution of which can be seen from the formula a on H for the preparation of oxazines, thiazines or azines, to intermediates containing one or more o'xyallryl groups attached'to nitrogen.

The standard reactions for the manufacture of oxazine dyestufi's are as follows: A.

nitroso derivative of an hydrox alkyl-arylamine or of an hydroxya-lky -alkyl-a lamine may be condensed with a pheno ic compound; or a nitroso derivative of a m-hydroxy-h droxyalkyl-arylamine or of ainshydroxy ydroxyalkyl-alkyi arylamine may be condensed with an ar lamina, with an alkyl-arylamine, with an hydroxyalkyl arylamine, or with an hydroxalkyl-alkylarylamine. Or again, the nitroso'derivative' of an alkyl-arylamine' may 'be; condensed t with a meta hydroxyhydroaya lkyl-arylalkyl-alkylarylamine.

amine or with a" meta=hy droxy-hydroxyv:

The standard reactions for the manufacr ture of thia zine dyestuffs are as follows; A

nitroso derivative ofian hydroxyalkyLaryl-i amine or of an hydroxyalkyl-alkyl-aryl amine may be converted into the corresponding p-diamine thiosulpho'nic acid by treatment with thiosulphate in the usual manner, j

and this oxidized together with an alkyl-arylamina, an hydroxyalkyl-arylaniinc, or an.

ziydrox alkyl-alkyl-aryl'amine. Or a ain,'a p-diamme thiosulphonic acid ohtaine from a p-nitroso-alkyl-arylamine may be oxidized together with an h droxyalkyl-arylamine or an hydroxyalkyl-akyl-arylamine.

The standard reactions for-the manufacture of azine dyestufi's are as follows: A 'nilrcso derivative of an hydronyalkyl-aryl- In an analogous manner either ordinary alkylated gallocyanines, or the hydroxya kylated allocyaninesmentioned in Examples 1 an 2 above, or gallocyanines containing both hydrox 'alkyl and alkyl groups may be condense with unsymmetrical dihydroxyalkylp=diannnes', the products having the great advantage that by adjusting the number of the hydroxy groups the solubility in water canb'e increased-to any extent dosired. Hydroxyalkylated gallocyanines can also be Condensed wi or phenols. V I

. Example 4.'-Hydroxyethyl-diethyl-dianr ino-naphtho-phenoxazoniuin chloride.

th primary aryla'mines' 25 parts of nitroso-diethyl-in-arnin'ophenol hydrochloride and 15 parts of hydroxyethyl alpha naphthylamine hydrochloride (prepared according to D. RP. 1630l3 by condensation v of alpha-naphthylamine with ethylene chlorhydrin) or the corresponding quantity of pure base, are boiled together in 300 parts of ethyl alcohol for about one hour. Reaction is complete when a drop spotted on filter paper no longer shows a green rim.. About 11 parts of. 55% zinc chloride solutionis then added and the 'solution allowed'to stand for at least 24 hours,

'- crystallization being slow. The dye is then collected, washed with a little alcohol and air-dried. It is obtained as bronzycrystals or powder. It dyes tannined cotton almost the same shade as-Nile blue 2 but possesses the advantage over the latter of greatly increased solubilit Example '5.-- ihydroxyethyl' benzyl diamino-naphtho-phenoxazonium chloride.

. water and added to the alcoholic soiuti0n' in small portions over a period of 4 hours with mechanical stirring. The solution is stirred a further two' hours, the temperature raised to 50 C., the salt produced in the nitrosatien filtered out and Washed clean with alcohol. The nitroso solution so obtained is added to a warm solution of 20 parts of benzyl-al'pha-naphthylamine in 50 parts of alcohol and the total volume made Y up to 272-300 parts of alcohol. On refluxing this solution for about an hour the reaction is completed and the dye-stu'tf be- ,dyestufl' is readily soluble in water and dyes tannined cotton nearly thesame shade as y or hydroxyalkyl-alkyl-nior I gins to separite' asv green crystals. Afterstanding for 24 hours, it is collected, washed \vith a small quantity of alcohol and obi tained as amass of green crystals. The

the preceding example.

- The (li-hydroxyethyl-m -aminohenolemployed is easily'prepared accor ing toD. f

l. I. 163043 by boiling m-amino-phenol with excess of aqueous'ethyl'ene chlorhydrin together with the theoretical amount of 1 chalk necessary to remove the hydrochloric acid produced, concentrating, and extract mg with butyl alcohol followed by the re above, may be condensed in the same manner ith 1-1.8 parts of hydroxyethyl-alphanapnthylamine, or with 13 parts of alpha-" naphthylamine to give ver soluble bright blue 7 dyes.

. l v nocin un.c.u, on, cn.ui

14.4 parts of @maphthol are dissolved in 50 parts of ethyl alcohol and to the boilin solution is added a solution in 50 parts 0 ethyl alcohol of 33.4 'parts'of-nitroso-hydroxyethyl-o-toluidine hydrochloride during a period of one hour, The solution is refluxed for a further hour and allowed to cool. The dye crystallizes in messes of bronzy needles. It is readily soluble inwaterand'dves tannined cotton inredder shades than Meldolas blue.

Azinea;

Example 7.-Hydroxyethyl dia mino P tolyl-tolazonium chloride. v

h I 1x no.mom ;.can on,i dn; cm xn,

21.2 parts of p-tolylamino-o-toluidine are dissolved in'300 parts of ethyl alcohol and the solution cooled to 05 C. Tothis solution is added with stirring, 33.4 parts of nitroso hydroxyethyl o toluidine' hydrochloride. in about an hour; the solution is then refluxed" for a further hour.. The dyestuiT crystallizes on cooling and is obtained as a red powder. It is very readily soluble in 130 Further, di iydroxyethyl-m-' Y aniino-p-cresol may beconverted to the-nilndamine formation is complete water and dyes tannined cotton in fast scarlet sh 30.2 parts of 4-p-tolyl-2-benzyl-toluylenem-diamine are dissolved in. 1,000 parts of alcohol and the solution cooled to, 0-5 C.

- 33.4 parts of nitroso-hydroxyeth-yl o-tolui-j dine hydrochloride are added to this solution with stirring. \Vhen indamme formation. is complete. the solution is refluxed and finally the solvent distilled ofi' until the vol- 'urne is reduced to'100 The dyest'ufl' crystallizes on cooling eing as a dark red crystalline mass; It is more soluble than'brilliant rhodulin'e red and dyes the same shade.

thus obtained diamino-phenazonium chloride.

(clii i.n.c.n. am.nn.cn .on

anion 9.8 parts of sym-dihydroxyethylii-phenylenediainine, prepared byboiling a solution of m-phenylene diamine with ethylene chlor- Ewample .9.Dihydroxvethyl-dimethylhydrin in presence of chalk, .aie dissolved in parts of water and 14 partsofnitrosodimethylan-ilin'e hydrochloride added slowly to the cooled solution.- This is then gradually heated to 80 C. and held at this tem- 'perature until the conversion of'indamine to azine is 'complete.' After cooling, zinc chloride and salt solution are added whereby the v dyestufi is obtained as its zinc chloride double salt. It is a dark powder with bronze reflex, dyeing tannined cotton a violet shade.

-' Example 10.--Dihydroxypropyhdimethyldiamino-phenazonium chloride.

12.8 parts of sym-dihydroxypropyl-mphenyleue diamine are dissolved 60 parts are added. When indamine to 4 hours. The'd obtained as a dark of .water and 14 parts of nitrOSddiinethEl- Q aniline added to the cooled solution.

is then gradually heatedto 80 C. until conversion of the indamine is complete when the dyestutf' is collected after adding zinc chloride and salt. It has the same proper ties as the product of Example 9, except that it has a higher solubility.

The sym-dili ;droizypropyhm-phenylene diar'nine employed in this preparation is prepared by boiling a solution of glycerol monochlorhydrin with m-phenylene diam'ine in the presence of the-exact amountof'. chalk necessary produced. wample J1. --Hydroxyethyl (ii-methyl diamino-phenazonium chloride.

to remove the-hydrochloric acid and to the cooled solution 21.1 parts of iaitroso-hydroxyethyl'aniline hydrochloride formation is complete, the solutionisheated to 80 C. andheld at that temperature until the Mine has been formed. The dyestufi is salted-out 13.2 parts of sym-dimethyl-m-phenylenel I diamine are dissolved in dilute acetic acid.

and obtained as a dark powder'which'lyes taunined cotton in purple shades.

The nitroso-hydroxyethyl-aniline is piepared in a similar manner to the nitrosohydroxyethyl-o-toluidine mentioned in EI- ample 1.

E ram Ze 12.--Dihydroxyethyl-axninwhy droxyenazonium chloride.

3 parts of nitroso-phenol are dissolved in QOO-Parts of water and'mixed with a solution of 8.1 parts of symdihydroxyethyl-mphenylene diamine in 200 parts of water. 25 parts of glacial acetic acid are added and the whole heated'on' the water-bath for 3 estufl' separates on coolin'g, vand after col ccting anddrying it is ruined, cotton purple but is chiefly valuable as an intermediate for other colouringmatters. r

' Tw in.

Erample 1 8. -D' dydmxyethyhdianlinm p toluth'iazonium chlori no.n.w.c.mgca, qnucaouaomoa a 16.8 parts ofnitroeo-hydroxyethyl-opowder. It dyes tan-1, i

5 48 arts of .sodiunitbiosulphate are dis- 1,ee1,147 U.

toluidine hydrochloride are dissolved in 100 a parts of dilute hydrochloric acid and reduced with zinc' dust. The colourless neutral" solution is'filteredfrom unused zinc 5 Iand'tra-nsferr'ed to a vessel in which it can be stirred and rapidly heated by injected steam. There-is then added to it in succession with stirring-25 parts of 50% zinc chloride so1ution,1 part of concentrated sul- Ju phuric acid. 9.5 parts ofaluminum sulphate dissolved in parts of, water, 13 parts of sodium thiosulphate dissolved in 15 parts of water, and 455 parts of sodium dichromate dissolved in .7 parts of water.- By means'of Listeam the temperature is, rapidly raised to 40 C. and then there is added 7.5 parts of hydroxyethyl-o-toluidine dissolved in 7 arts of concentrated hydrochloric acid fol owed by 9.5 parts of sodium bichromate in 15 arts of water. The temperature is raised to 0 G and 8.9 parts of 70% manganese dioxide as afine paste is added. after which the temperature 1s again raised to 85 C.

i I and maintained therefor minutes.- After '2 ooolingfto30 0., 15- farts of concentrated v sulphuric acid are ad ed, and after further the crystalline zinc chloride double salt 9 the dyestufi is collected anddried.

It is a bronze powder, readily soluble in 30 water and dyeing tannined'cotton a reddish.

shade of blue.

In the same manner, using equivalent parts, other hydroxyalkyl-asym-p-diamines can be condensed with hydroxyalkylaryl- 36 amines or alkylarylamines, and conversely m-dialkyl-p-diamines may be cond yin hydroxy l-aryiamines.

Example 14.- ternal salt of hydroxyethyl-ethyLamino-l 2 4 naphtho-phenthiazine.

Or -05H OR) Hal at on I solv in 400 parts of water and to this are added a solution containing ltl parts-oi i;-itroso-hydroxyethybethybaniline hydrochloride followed byparts of 30% acetic 'acid.- The mixture is stirred at 8D C. for

an-hou r' andfth'en a aste of 16.7 parts of nitroso-S'chaefler aci with continued'stirring, then, after add' 51. 100 parts of sal .it'is increased to 50 C. for

.35 hourgitobof Jeri, hours, were C. for

the warm solution. The filter cake is dis- 60 solved in dilute caustic soda, filtered, rea

'stufi's of the constitution derived from the following dihydroxyflsulpho is added at 36 0; p l This temperatuneis' maintainedfor 8 hours v 4 hours-and finally-M80? C. for-3 hours. 1 The dyestufi' which separates is filtered from The above mentioned nitroso-hydroxyethyl-ethyla-niline is obtained from the hy-- droxyethyl-ethylaniline of .D. R. P. 163043 by dissolving 8 parts in 15 parts of. concentrated hydrochloric acid and adding a strong solution of3.5 parts of sodium 'nitrite with strong cooling. The nitroso-h. I dr 0 x yethyI-eth laniline hydrochlori e separates as a st-i mass of minute yellow crystals which are collected, pressed and dried. I

What we claim and desire to secure by Letters Patent is:--

1. The recess of manufacturing dyee quinonimide class possessing formula-'- in. which A stands for nitrogemoxygen or sulphur, by applying a standard'reaction for the preparation of oxazines, thiazines and azines, to intermediates containat M least one hydroxyalk l group attach in which for oxygen nitrogen or sulphur, withat least one aminb on with 0 an hydroxyalkyl group attache to 1t attached' to at least one of the benzene rin and which are readily converted into solu 1e acid sulphate dyestuffs. by treatment with concentrated sulphuric acid, which d estu-fl's yahydrolysisreadily split off su phuric ac: '3.- The new'oxazine d estufl's possessing I the constitution indicate by the ;.o llowing formula-,-

with at least one amino group an hydroxyalk'yl group. attached to at least one of the benzene ring, and which on treat? ment with sulphuric acid gives a soluble acid 128 dye t fi; m ly, hydroxy-ethyl-diethylwhich is readily conierted into the acid dmmino-naphtho-phenoxazonium .chlonde sulphate dy stnfi b t t t ith onwith the constitution indieated by the fol- .centrnted sulphuric acid and this acid sull5- E ric ether splits ofi sulphuric acid on .-ydrolysis.

n testimony whereof We have signed our name's t'o thiss pecification. I

lowing formula 1o v (0.1mm ARTHUR GEORGE GREEN.

- KENNETH HE B RT SAUNDERS.

ERNEST BRYAN 

